KR101958996B1 - A method for preparing membrane having nano-sized pore for water treatment and membrane prepared using same - Google Patents

Abstract

The present invention provides a method of producing a porous polymer film, comprising: immersing a porous polymer film supporting layer having a first pore in a first polymer containing solution; Immersing the support layer in a non-solvent to solidify the first polymer to form a first polymer layer that fills voids present on a surface or a cross section of the support layer to hydrophilize the support layer; And preparing a membrane having a second nano-sized pore smaller than the first pore by providing a second polymer layer by pressing the supporting layer having the first polymer layer formed thereon by dipping it in a second polymer-containing solution, Wherein the support layer is hydrophobic and the first and second polymer layers are hydrophilic, and a nanocomposite membrane for water treatment prepared thereby. According to the present invention, it is possible to provide a membrane in which the impurity separation ability is greatly improved by hydrophilizing the hydrophobic support layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nano-scale membrane for water treatment, and a method for preparing the same,

The present invention relates to a method for manufacturing a water treatment membrane including nano-scale pores and a water-treatment nano-scale membrane produced thereby.

Removal of impurities contained in photoresist solutions used in semiconductor processes is becoming increasingly important. The impurities in the photoresist solution are mainly composed of metal particles and organic agglomerated particles, and current commercialized membranes are problematic because impurity removal in the photoresist solution is not sufficient.

Currently, polymer membranes with excellent chemical durability, such as nylon or polyolefin, have been used but are not known to have high purity. In the case of using a polyolefin membrane, the metal particles in the impurities can be removed by the pore size of the membrane, but the organic aggregate particles must be removed by adsorption in the process of contacting the particles with the whole pore size as well as the pore size. It can not be separated by a mechanism due to adsorption. The nylon membranes are generally made by vapor-induced phase separation (VIPS), and it is known that the nylon membranes thus prepared are difficult to manufacture with nanoparticles. In addition, the nylon membrane has a polarity higher than that of a polyolefin membrane, but has a limitation in that it is not easy to remove organic aggregate particles because the contact time with impurities is short.

On the other hand, the present inventors have found that when the pores of the conventional polyolefin membrane are produced in the nano-scale, the pore size is largely reduced while the contact time with the impurity particles is greatly increased, and the removal efficiency of the impurities is greatly increased. Therefore, it is an object of the present invention to provide a method of manufacturing a membrane having a pore size reduced by filling a void of the polyolefin membrane while using a conventional polyolefin membrane having macropores so as to provide a membrane having improved impurity removal efficiency applicable to general water treatment and semiconductor processing And membranes.

It is an object of the present invention to provide a method for producing a water-treating nanocomposite membrane and a membrane produced thereby.

It is another object of the present invention to provide a method for manufacturing a nanocomposite membrane for water treatment capable of greatly improving the removal efficiency by forming nano pores using a hydrophobic support layer having a large pore and a plurality of polymers, .

Still another object of the present invention is to provide a method for manufacturing a nanocomposite for water treatment in which the surface of the hydrophobic support layer is hydrophilized while filling voids existing on the surface and the cross section of the hydrophobic support layer, and a membrane produced thereby.

According to a first aspect of the present invention, there is provided a method of manufacturing a porous polymer film, comprising: immersing a porous polymeric film supporting layer having a first pore in a first polymer containing solution; Immersing the support layer in a non-solvent to solidify the first polymer to form a first polymer layer that fills voids present on a surface or a cross section of the support layer to hydrophilize the support layer; And preparing a membrane having a second nano-sized pore smaller than the first pore by providing a second polymer layer by pressing the supporting layer having the first polymer layer formed thereon by dipping it in a second polymer-containing solution, Wherein the support layer is hydrophobic and the first and second polymer layers are hydrophilic.

The second polymer may be interfacially polymerized and coated on the surface of the support layer and the first polymer layer.

Also, the support layer may include polyethylene, polypropylene, and a combination thereof. The first polymer layer may include poly (vinyl alcohol-co-ethylene) (EVOH) The second polymeric layer may comprise a polyamide, a polyurethane, and combinations thereof.

According to a second aspect of the present invention, embodiments of the present invention include a porous polymeric film support layer having a first pore; A first polymer layer provided on an outer surface of the support layer and filling a void existing in a surface or a cross section of the support layer to hydrophilize the support layer; And a second polymer layer provided to cover the support layer and the first polymer layer, wherein the membrane has a second pore having a nano-size smaller than the first pore, the support layer is hydrophobic, The first and second polymeric layers comprise a water-treating nanocomposite membrane prepared according to embodiments of the first aspect which are hydrophilic.

According to a third aspect of the present invention, another embodiment of the present invention includes a water treatment apparatus comprising a water treatment nanocomposite membrane according to the second aspect and removing impurities.

According to a fourth aspect of the present invention, there is provided a method of reusing a photoresist solution containing impurities in a semiconductor process, comprising: preparing a water-treating nanocomposite membrane according to the second aspect; And removing impurities including metal particles and organic agglomerated particles in the photoresist solution by using the water-treatment nano-scale membrane.

As described above, according to the present invention, it is possible to provide a method of manufacturing a nanocomposite membrane for water treatment and a membrane produced thereby.

Also, according to the present invention, there is provided a method for manufacturing a water-treating nano-scale membrane capable of greatly improving removal efficiency by forming nano pores using a hydrophobic support layer having a large pore and a plurality of polymers, and a membrane produced thereby .

Also, according to the present invention, it is possible to provide a method for manufacturing a water-treating nano-scale membrane in which the surface of the hydrophobic support layer is hydrophilized while filling voids existing on the surface and the cross section of the hydrophobic support layer, and a membrane produced thereby.

1 is a flowchart illustrating a method of manufacturing a nanocomposite membrane according to an embodiment of the present invention.
2 is a schematic view of a water treatment nanocomposite membrane according to an embodiment of the present invention.
3 is a SEM photograph of a supporting layer according to an embodiment of the present invention.
4 is a SEM photograph of a membrane having first and second polymer layers on a supporting layer according to FIG.

The details of other embodiments are included in the detailed description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the exemplary embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, Like parts are denoted by the same reference numerals throughout.

Hereinafter, the present invention will be described with reference to the drawings.

1 is a flowchart illustrating a method of manufacturing a nanocomposite membrane according to an embodiment of the present invention.

Referring to FIG. 1, a method for fabricating a nanocomposite membrane according to an embodiment of the present invention includes: (S10) immersing a porous polymeric film support layer having a first pore in a first polymer-containing solution; (S20) of immersing the support layer in a non-solvent to solidify the first polymer to form a first polymer layer that fills voids present on the surface or cross section of the support layer to hydrophilize the support layer; And a step of preparing a membrane having a nano-sized second pore smaller than the first pore by providing a second polymer layer by dipping the supporting layer having the first polymer layer in a second polymer-containing solution, S30). At this time, the support layer may be hydrophobic, and the first and second polymer layers may be hydrophilic.

According to an embodiment of the present invention, a nano-scale pore size can be formed by the method of manufacturing a nanocomposite membrane for water treatment, thereby providing a membrane having a greatly improved removal efficiency of impurities and the like.

In the step (S10) of immersing the porous polymeric film support layer in the first polymer-containing solution, the support layer may be in the form of a film made of a porous polymer, and the support layer may be hydrophobic and the first pore may be a macropore . ≪ / RTI > Next, in the step (S20) of forming the first polymer layer, the first polymer contained in the first polymer-containing solution may be solidified by immersing the support layer in which the first polymer-containing solution is immersed in the non-solvent. The solidified first polymer may be formed as a first polymer layer by filling voids present on a surface or a cross section of the support layer, and the first polymer layer may hydrophilize the hydrophobic support layer.

The non-solvent may be a solvent which does not dissolve or swell the polymer until the melting point of the polymer or the boiling point of the liquid, preferably water. The non-solvent may induce solidification of the first polymer contained in the first polymer-containing solution, and the solidified first polymer may fill the pores of the support layer on the surface of the support layer, And may be provided as a discontinuous layer on the surface of the support layer. For example, the first polymer layer may be provided in the first pores of the support layer to reduce the volume of the first pores. The first polymer layer may be provided to expose at least a part of the surface of the support layer. In addition, the first polymer layer may be provided so as to be impregnated into the support layer with the first polymer-containing solution so as to be fixed in the surface and the cross section of the support layer. Therefore, in the course of using the membrane for removing impurities, the first polymer layer is not lost, and the pores on the surface and the cross-section of the support layer can be stably reduced, so that the impurity removal efficiency of the membrane can be improved.

In the step (S30) of forming the membrane having the second pores, the support layer on which the first polymer layer is formed may be immersed in the second polymer-containing solution, followed by pressing to form the second polymer layer. The second polymer layer may be provided on the outer surface of the support layer and the first polymer layer so as to cover the support layer and the first polymer layer as a whole and have a second pore. The second polymer layer may be formed by interfacial polymerization of a second polymer in the second polymer-containing solution on the surface of the first polymer layer, and may be coated on the surface of the support layer and the first polymer layer .

A method of manufacturing a nanocomposite membrane for water treatment according to an embodiment of the present invention includes forming a first polymer layer and a second polymer layer by using a large pore, for example, a support layer having a first pore, Of the membrane having the second pore can be produced. The first pores may have an average size of 0.02 μm to 10.0 μm, and the second pores may have an average size of 1 nm to 5 nm.

In addition, the support layer may be hydrophobic, and the first and second polymer layers may be hydrophilic. The porous polymeric film support layer may be formed of a hydrophobic polymer as a film-like support layer. Membranes prepared according to embodiments of the present invention include a hydrophobic support layer, but the surface of the membrane may be hydrophilic.

For example, the support layer may comprise polyethylene, polypropylene and combinations thereof, wherein the first polymer layer comprises poly (vinyl alcohol-co-ethylene) (poly (vinyl alcohol-co-ethylene) The second polymeric layer may comprise a polyamide, a polyurethane, and combinations thereof.

The support layer may be made of polyethylene or polypropylene, but is not limited thereto. For example, the support layer can be obtained by using a commercially available porous polymeric film support layer known in the art. The support layer may be formed in the form of a porous polymer film, and is preferably not damaged when impregnated into a solution containing a first polymer such as poly (vinyl alcohol-co-ethylene).

In general, polyolefin-based membranes such as polyethylene and polypropylene are excellent in chemical durability. However, when impurities including organic aggregate particles are removed by using such a material as a membrane, there is a disadvantage that the purification purity is not high. For example, the organic agglomerated particles are not easily removed by the method of removing particles using pores of the membrane, and when the membrane and the organic agglomerated particles are in contact with each other, the membrane adsorbs and removes the organic agglomerated particles However, the polyolefin-based membrane has no polarity on its surface, so that it can not be separated into a mechanism by adsorption.

On the other hand, according to the method of manufacturing a nanocomposite membrane for water treatment according to an embodiment of the present invention, a support layer containing polyethylene or polypropylene is used, and the first and second polymer layers are provided on the surface of the support layer in a novel manner Thereby ensuring excellent chemical durability and providing the surface of the membrane with hydrophilic property. Also, the membrane manufactured according to the method of manufacturing a nanocomposite for water treatment according to an embodiment of the present invention may include a nano-sized second pore although it includes a supporting layer having a micro-sized first pore. The second polymer layer together with the first polymer layer on the membrane may be provided to cover the support layer so that the size of the cross section of the first pore of the support layer can be reduced so that the membrane has a smaller size than the first pore Of the second pore.

Therefore, the membrane manufactured according to the embodiment of the present invention has excellent chemical durability and polarity on the surface, so that impurities including both metal particles and organic aggregated particles can be easily removed. In addition, the method of manufacturing a membrane according to an embodiment of the present invention can easily produce a membrane having a nano-pore size and can easily remove fine impurities due to the nano pore size of the membrane. Therefore, The efficiency can be improved.

The average size (diameter) of the first pores of the porous polymeric film support layer may be 0.02 mu m to 10.0 mu m. If the average size of the first pores is less than 0.02 탆, the first polymer-containing solution hardly penetrates into the surface and the cross-section of the support layer, and if the average size of the first pores exceeds 10.0 탆, So that it acts as a defect on the surface side, and the removal efficiency of impurities and the like may not be high.

In the step of forming the first polymer layer (S20), the support layer may be impregnated with a poly (vinyl alcohol-co-ethylene) polymer-containing solution to form the polar polymer layer. When the first polymer layer contains poly (vinyl alcohol-co-ethylene), the content of ethylene may be from 20 mol% to 50 mol%. In the first polymer-containing solution containing the poly (vinyl alcohol-co-ethylene) polymer solution, the first polymer may be dissolved in dimethylsulfoxide. The support layer impregnated with the first polymer-containing solution may then be immersed in a non-solvent (water) to solidify the first polymer. The membrane may be fabricated such that the first polymer is impregnated into an end face of the support layer, and the first polymer may be stably fixed in the support layer.

The first polymer layer may be provided to cover at least a part of a surface or a cross section including pores of the support layer, and the support layer may be made hydrophilic. The hydrophilic second polymer layer provided on the first polymer layer and the support layer may be easily bonded to the support layer without repulsion with respect to the support layer by hydrophilizing the hydrophobic support layer in the first polymer layer .

The first polymer-containing solution may penetrate the surface and the cross-section of the support layer and then be solidified by the non-solvent to provide the first polymer layer. The first polymer-containing solution may comprise poly (vinyl alcohol-co-ethylene) (poly (vinyl alcohol-co-ethylene)).

The content of the first polymer may be 5 wt% to 20 wt% based on 100 wt% of the total amount of the first polymer-containing solution. If the content of the first polymer is less than 5 wt%, the content of the first polymer is insufficient, so that the surface or the cross section of the support layer is not sufficiently hydrophilized, so that the first polymer layer can not be well bonded on the support layer . When the content of the first polymer is more than 20% by weight, the first polymer layer can completely cover a part of the first pores of the support layer, and the second pores of the prepared membrane are partially clogged, .

The mole percent of ethylene relative to the total mole percent of the poly (vinyl alcohol-co-ethylene) can be from 20 mole percent to 50 mole percent. The poly (vinyl alcohol-co-ethylene) may be represented by the following chemical formula, and may be a copolymer made of vinyl alcohol having polarity and ethylene having no polarity with respect to the vinyl alcohol.

The poly (vinyl alcohol-co-ethylene) is a poly (vinyl alcohol-co-ethylene) in which the mole% (n) of the ethylene relative to the total mole% (m + Vinyl alcohol-co-ethylene) is so high that it is not fixed on the support layer due to the action of repelling each other with the hydrophobic support layer, so that it is difficult to hydrophilize the support layer. When the molar% (n) of ethylene is more than 50 mol%, the overall polarity of poly (vinyl alcohol-co-ethylene) is lowered and can be stably fixed on the support layer. However, The bonding strength between the support layer and the hydrophilic second polymer layer provided on the first polymer layer is lowered and it is difficult to provide a stable membrane.

Thus, the poly (vinyl alcohol-co-ethylene) may be a poly (vinyl alcohol-co-ethylene) copolymer that can fix the second polymer layer while hydrophilizing the support layer between the hydrophobic support layer and the hydrophilic second polymer layer. (N) is preferably 20 mol% to 50 mol% based on the total mol% (m + n) of the ethylene.

In the method of manufacturing a membrane according to an embodiment of the present invention, the support layer on which the first polymer layer is formed may be dipped in the second polymer-containing solution and then compressed. The method of manufacturing a membrane according to an embodiment of the present invention may include a step S30 of forming a membrane having the support layer and the second polymer layer on the first polymer layer. In addition, the membrane may be provided with a second pore having a nano-size smaller than that of the first pore of the support. For example, the second polymer layer may be formed by interfacial polymerization after the first polymer layer is formed, and the first polymer layer may include polyamide, polyurethane, and combinations thereof.

By the method of manufacturing a membrane according to an embodiment of the present invention, a first polymer layer and a second polymer layer including, for example, polyamide, polyurethane and combinations thereof, are formed on a support layer comprising polyethylene, polypropylene, Thereby providing a membrane provided with the membrane. The membrane has a mechanical strength due to chemical and physical environment by the support layer and can have a polarity by the first and second polymer layers. Therefore, the impurities are removed by adsorbing impurities in the wastewater or solution can do. The method of manufacturing a membrane according to the present invention may further include the step of providing a first polymer layer capable of hydrophilizing the support layer between the hydrophobic support layer and the hydrophilic second polymer layer. The first polymer layer is sandwiched between the support layer and the second polymer layer so that the support layer and the second polymer layer can be stably fixed to each other and fixed, thereby improving the mechanical strength of the membrane.

The method for manufacturing a membrane according to an embodiment of the present invention comprises impregnating the first polymer-containing solution on the surface and cross-section of the porous polymeric film support layer having an average size of the first pores of 0.02 탆 or more, preferably 0.02 탆 to 10.0 탆, And a second polymer layer containing polyamide or polyurethane is formed thereon using the second polymer-containing solution. The prepared membrane may have a second pore having an average size of 1 nm to 5 nm.

The support layer may include polyethylene or polypropylene. The polyethylene and the polypropylene are expensive to form into nano-sized pores. In addition, since the nano-sized pores are formed in the polyethylene and the polypropylene, It is not easy. On the other hand, in the method of manufacturing a membrane according to the present invention, a membrane is manufactured using the support layer, and the surface of the first polymer layer provided on the support layer is subjected to interfacial polymerization to form a second nano- May be provided to have pores. The membrane on which the second polymer layer is formed may have a thickness of 1 nm to 5 nm.

The second pore of the membrane may have an average size (diameter) of 1 nm to 5 nm. When the average size of the second pores is less than 1 nm, the size of the pores of the membrane is too small, and when used for water treatment, the pores of the membrane are often blocked by impurities, which may be a problem. When the average size of the second pores is more than 5 nm, the pores provided in the membrane are too large to easily remove the impurities to be removed. The method for producing a nanocomposite membrane for water treatment according to the present invention can provide a method for efficiently producing a membrane in which the average pore size of the membrane is uniformly formed within a predetermined range of 1 nm to 5 nm.

That is, the present invention provides a hydrophobic porous polymeric film support layer having macropores having an average size of the first pores of 0.02 占 퐉 or more on the surface and cross-section, such as poly (vinyl alcohol-co-ethylene) And forming a second polymer layer containing polyamide, polyurethane or the like through interfacial polymerization on the first polymer layer, thereby providing a membrane having a nanoparticle second pore. In the process of using the membrane for water treatment, the removal efficiency of impurities such as fine aggregates of organic particles with the metal particles is greatly improved.

2 is a schematic view of a water treatment nanocomposite membrane according to another embodiment of the present invention.

Referring to FIG. 2, a water treatment nanocomposite membrane 100 according to an embodiment of the present invention includes a porous polymeric film support layer 110 having a first pore; A first polymer layer 120 provided on the outer surface of the support layer 110 and filling the voids present on the surface or the end surface of the support layer 110 to hydrophilize the support layer 110; And a second polymer layer 120 provided to cover the support layer 110 and the first polymer layer 110. The membrane 100 has a second pore size smaller than the first pore size, , The support layer 110 is hydrophobic, and the first and second polymer layers 120 and 130 are hydrophilic and can be manufactured according to the above-described embodiment.

The second polymer layer 130 may be coated on the surface of the support layer 110 and the first polymer layer 120 by interfacial polymerization. The supporting layer 110 may have a first pore having an average size of 0.02 μm to 10.0 μm and may include a first polymer layer 120 and a second polymer layer 130 provided on the supporting layer 110 The membrane 100 of the present invention may have a second pore having an average size of 1 nm to 5 nm.

The support layer 110 may include polyethylene, polypropylene, and combinations thereof. The first polymer layer 120 may be formed of poly (vinyl alcohol-co-ethylene) And the second polymer layer 130 may comprise polyamide, polyurethane, and combinations thereof.

Since the membrane 100 according to the embodiment of the present invention has nano-scale pores, the removal efficiency of impurities can be greatly improved. The membrane 100 is made of a polyolefin having macropores of 0.02 占 퐉 or more as the hydrophobic porous polymeric film support layer 110 and a polymeric layer capable of impregnating the surface and cross section of the support layer 110, A polymer layer such as poly (vinyl alcohol-co-ethylene) can be used. Further, by forming the second polymer layer 130 through interfacial polymerization at the surface of the first polymer layer 129 (containing poly (vinyl alcohol-co-ethylene)), the size of the first pores of the support layer 110 To thereby provide a membrane having a second pore which is a nano-scale pore.

That is, the present invention provides a hydrophobic porous polymeric film support layer 110 having macropores having an average pore size of 0.02 占 퐉 or more and a poly (vinyl alcohol-co-ethylene) polymer layer And a polyamide layer or a polyurethane layer which is a second polymer layer is formed thereon through interfacial polymerization to provide a membrane 100 having nano pores and greatly improved impurity removal efficiency.

According to another embodiment of the present invention, the membrane may include a porous polymeric film support layer having a first pore and first and second polymer layers sequentially disposed on the surface of the support layer. The first polymer layer may be impregnated into the surface and the end surface of the support layer and solidified by the non-solvent to be provided on the inner surface of the first pore and on the surface of the support layer, and the second polymer layer may be provided on the first polymer layer Lt; / RTI > The surface of the support layer may have a surface roughness, and the second polymer layer may be provided on the support layer to cover the surface roughness. The surface roughness provided on the surface of the support layer can increase the surface area of the support layer and can uniformly provide the first polymer-containing solution on the support layer. The second polymer layer may be provided to cover the surface roughness of the support layer. The surface roughness of the support layer can improve the mechanical strength of the membrane by allowing the first polymer layer and the second polymer layer, which are sequentially provided on the support layer, to physically bond well.

For example, the water-treating nanocomposite membrane according to the present invention can remove impurities in the photoresist solution in a semiconductor process. The nano-scale membrane for water treatment according to the present invention may have predetermined chemical and physical strength due to the support layer, and the outer surface may be hydrophilic due to the first and second polymer layers, and the nano- It is possible to easily remove impurities such as metal particles and organic aggregate particles contained in the photoresist solution in the semiconductor process.

A nano-scale membrane (composite membrane) for water treatment according to the present invention is a water treatment apparatus for removing impurities, specifically, a wastewater treatment apparatus for a semiconductor process, an ultrapure water purification apparatus for a semiconductor process, a water purifier, a pretreatment apparatus for a seawater desalination process, A treatment device, a wastewater treatment device, a food purification device, or the like.

In the present invention, the water used for the water treatment may be an organic solvent such as ultrapure water, wastewater, photoresist solution, or seawater. The impurities may be metal particles and organic aggregate particles in a photoresist solution in a semiconductor process.

The nanocomposite membrane for water treatment according to the present invention can be used in a method of reusing a photoresist solution containing impurities in a semiconductor process. The method of reusing the photoresist solution is similar to that of the water treatment nanocomposite membrane ; And removing the metal particles and the organic agglomerated particles in the photoresist solution by using the water treatment nanocomposite membrane.

The water-treating nano-scale membrane can remove metal particles and organic aggregate particles from the photoresist solution by pore size, and adsorb and remove the organic aggregate particles by the membrane.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.

Example  1: Compound Membrane  Produce

In order to prepare a support layer impregnated with poly (vinyl alcohol-co-ethylene) (hereinafter referred to as EVOH) on a polyethylene film (average pore size 0.03 micron, SK Innovation), 10 wt% of EVOH (ethylene 27 mol% A polymer solution dissolved in 90 wt% of the side was prepared, and the polyethylene film was immersed in this solution. After immersing for 10 minutes, the polymer solution was uniformly coated on the front and back surfaces with a roller, immersed in water of 20 degrees to solidify the polymer solution, and the solvent was removed to complete the support layer membrane. The prepared support layer membrane was immersed in an aqueous solution (m-phenylene diamine (2 wt%), trimethylamine (1 wt%), camphorsulfonic acid (2 wt%)) for 1 minute, (0.1% by weight) and isolC (99.9% by volume) for 1 minute, dried at room temperature for 4 minutes, and then coated with a polyamide layer (second polymer layer) Membranes were evaluated.

Example  2: Compound Membrane  Produce

The same procedure as in Example 1 was carried out except that 5 wt% of EVOH was used in Example 1 above.

Example  3: Compound Membrane  Produce

The procedure of Example 1 was repeated except that 15 wt% of EVOH was used in Example 1.

Example  4: Compound Membrane  Produce

The procedure of Example 1 was repeated except that the average pore size of the polyethylene film in Example 1 was 0.2 microns.

Example  5: Compound Membrane  Produce

Example 1 was carried out in the same manner as in Example 1, except that 32 mol% of ethylene was used as the EVOH.

Comparative Example  1: Manufacture of reverse osmosis membrane

A membrane was prepared in the same manner as in Example 1, except that a polyethylene film not impregnated with EVOH polymer was used as a support layer.

Experimental Example  One: Membrane  Performance evaluation

The permeate flow rate and NaCl removal rate of the membranes prepared in the above Examples and Comparative Examples were measured at 15 bar, and a NaCl removal rate was measured using a conductivity meter. The feed solution was a 0.2 wt% aqueous solution of NaCl.

The membranes prepared in the above Examples and Comparative Examples were subjected to the particle removal rate by using the following equation and the results are shown in Table 1 (measured pressure, 1 kgf / cm 2 ).

R (%) = (Cf - Cp) * 100 / Cf

R is the removal rate, Cf is the concentration of the undiluted solution, and Cp is the concentration of the permeate.

Permeate flow rate
(LMH) NaCl removal rate (%) Example 1 35 93 Example 2 38 93 Example 3 29 95 Example 4 48 92 Example 5 27 90 Comparative Example 1 5 72

In the case of Comparative Example 1 using only the hydrophobic polymer film, the permeation flow rate and the removal rate were both very low. However, the composite membrane according to Examples 1 to 5, which is a water treatment nano-scale membrane manufactured according to the present invention, The surface and the cross section are hydrophilized, so that the permeation flow rate and the removal rate are both increased as compared with Comparative Example 1.

Experimental Example  2: Membrane  Checking the site

FIG. 3 is a SEM image of a supporting layer according to an embodiment of the present invention, and FIG. 4 is a SEM photograph of a membrane having first and second polymer layers on a supporting layer according to FIG.

FIG. 3 is an SEM photograph of a supporting layer made of polyethylene. SEM photographs of large pores and the like are shown. In FIG. 4, the membrane in which EVOH and polyamide are formed on the polyethylene support layer has almost no macropores . The membrane according to FIG. 4 was confirmed to have pores smaller than the pores shown in FIG. 3 by sequentially providing EVOH and polyamide on the support layer.

100: water treatment nano-scale membrane 110: porous polymeric film support layer
120: first polymer layer 130: second polymer layer

Claims (13)

Immersing a porous polymeric film support layer having a first pore in a first polymer containing solution;
Immersing the support layer in the non-solvent to solidify the first polymer to fill the voids existing in the support layer to reduce the volume of the first pores and to form the first polymer layer to hydrophilize the support layer; And
Preparing a support having a first polymer layer formed thereon by immersing the support layer in a second polymer containing solution and pressing the polymer layer to form a second polymer layer having a second pore size smaller than that of the first pore; Including,
Wherein the support layer is hydrophobic and the first and second polymer layers are hydrophilic. The method according to claim 1,
Wherein the second polymer is interfacially polymerized to be coated on the surface of the support layer and the first polymer layer. The method according to claim 1,
Wherein the first pores have an average size of 0.02 탆 to 10.0 탆. The method of claim 3,
Wherein the second pores have an average size of 1 nm to 5 nm. The method according to claim 1,
Wherein the support layer comprises polyethylene, polypropylene and combinations thereof, wherein the first polymer layer comprises poly (vinyl alcohol-co-ethylene) (poly (vinyl alcohol-co-ethylene) Wherein the membrane comprises polyamide, polyurethane and combinations thereof. 6. The method of claim 5,
Wherein the content of the first polymer is 5 wt% to 20 wt% based on the total 100 wt% of the first polymer-containing solution. The method according to claim 6,
Wherein the molar percentage of ethylene relative to the total molar percent of the poly (vinyl alcohol-co-ethylene) is 20 mol% to 50 mol%. The method according to claim 1,
Wherein the surface of the support layer is provided with a roughness and the second polymer layer is provided to cover the surface roughness. A porous polymeric film support layer having a first pore;
A first polymer layer provided on an outer surface of the support layer to fill a void existing in the support layer to reduce a volume of the first pore and to hydrophilize the support layer;
And a second polymer layer provided to cover the support layer and the first polymer layer,
Wherein the membrane has a second pore size smaller than the first pore,
9. The nanocomposite for water treatment according to any one of claims 1 to 8, wherein the support layer is hydrophobic and the first and second polymer layers are hydrophilic. 10. The method of claim 9,
Wherein the water treatment nanocomposite membrane removes impurities in the photoresist solution in a semiconductor process. A water treatment apparatus comprising the nanocomposite membrane of claim 9 for removing impurities. 12. The method of claim 11,
Wherein the impurity comprises metal particles and organic agglomerated particles in a photoresist solution in a semiconductor process. A method of reusing a photoresist solution containing impurities in a semiconductor process,
Preparing a water-treating nanocomposite membrane of claim 9; And
Removing the metal particles and the organic agglomerated particles in the photoresist solution using the water treatment nanocomposite membrane.

Images